Cyanovinyl pyrethroids and pesticidal use thereof

ABSTRACT

The invention relates to novel substituted cyclopropanecarboxylic acid esters, and to methods of preparation thereof. The invention also relates to methods of use of the compounds for the control of insect pests of agriculturally important crops, and for the control of ectoparasites, especially acarina, of domesticated warm-blooded animals.

This is a continuation of application Ser. No. 937,360 filed Aug. 28,1978 now abandoned.

The invention relates to novel substituted cyclopropanecarboxylic acidesters, hereinafter also referred-to as "cyanovinyl pyrethroids",together with methods of use for the control of insect pests ofagriculturally important crops and of ectoparasites, especially acarina,of domesticated warm-blooded animals.

Control of the above insect pests of crops comprises applying aneffective amount of a compound of the invention to the foliage and stemsof the crops and/or to the soil in which these crops propagate and grow.Control of the ectoparasites, especially acarina, can be best achievedby contacting the ectoparasites with an effective amount of a compoundof the invention or by applying an effective amount of the compoundtopically to the host animal and/or treating their environment withsame. Alternatively, these compounds may be used for systemic control ofthe ectoparasites, especially acarina, comprising administering to thehost animal orally or parenterally an effective amount of thesubstituted cyclopropanecarboxylic acid esters of the invention. Thesenovel compounds may be represented and defined by formula (I) asfollows: ##STR1## wherein R₁ is ##STR2## R₂ is a moiety selected from##STR3## R₃ is hydrogen or methyl; X and X' are each selected fromhydrogen, halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy and haloalkyl C₁ -C₂ ; Yis selected from hydrogen, halogen, methyl or methoxy. It is recognizedof course, that the compounds represented by formula (I) above may existin a number of geometric and optical isomeric forms and mixturesthereof, and that varying degrees of insecticidal and acaricidalactivity would be expected to be associated with each isomer. Thoseisomers in which the carboxylic acid (ester) and the β-cyanostyrylfunctions are in the opposite sides of the cyclopropane ring aredesignated as trans; those in which they are on the same side aredesignated as cis. In each case, these may be separated into (+) and (-)optical isomers by appropriate methods, such as, for instance, the useof chiral bases in the separation of the carboxylic acid precursors (offormula IV) of the above formula (I) compounds. A further locale forgeometrical isomerism is the β-cyanostyryl function itself. In this casethe designation Z is given to those compounds in which the cyano andcyclopropyl substituents are on the same side of the carbon--carbondouble bond, whereas the E isomer is that in which the aryl orheterocyclic and the cyclopropyl substituents are so situated.

When the formula IV acids are esterified with α-cyano-m-phenoxybenzylalcohol, the resulting formula (I) esters have an additional chiralcenter. It is recognized that certain molecular species combiningspecial combinations of these geometrical and optical characteristicswill possess superior insecticidal and acaricidal activity. Theinvention includes all such combinations. Thus, the hereinabove definedcompounds of formula (I) may be the cis and trans cyclopropane isomers,the E and Z side-chain olefin isomers, the optical isomers thereof andthe isomeric mixtures thereof.

A preferred group of compounds represented by formula (I) above arethose wherein R₁ is selected from ##STR4## R₂ is selected from ##STR5##R₃ is methyl; the cis and trans cyclopropane isomers, the E and Zside-chain olefin isomers, the optical isomers thereof and the isomericmixtures thereof.

Among the economic losses caused annually by acarina, those attributableto the sub-order Ixodidae are of considerable importance. Ixodid ticksare responsible for the maintenance and propagation of a great manyhuman and animal diseases throughout the world. They are vectors for thediseases: tick paralysis and tick toxicosis. A single tick species cancause paralysis of several different mammals, and several tick speciescan cause paralysis in a particular host. Tick-borne diseases, such asSweating Sickness, Babesiosis, Anaplasmosis, Theileriosis andHeartwater, have been and are responsible for the death and/ordebilitation of a vast number of animals throughout the world each year.In point of fact, of all external parasites, ticks are responsible forthe greatest economic losses in livestock production in the world today.Such losses are, of course, attributed not only to death, but alsodamaged hides, loss in growth rate, reduction in milk production andreduced grade of meat animals.

The hereinabove described and defined compounds represented by formula(I) are eminently suitable for the control of Ixodidae. Control iseffected by means of ixodicidal and of chemosterilant activity which theformula (I) compounds exert upon the larvae, nymphs, and adult male andfemale ticks. This method of control is useful against Argasidae orIxodidae ticks, including, for example, those of the following types:Boophilus, Amblyomma, Anocentor, Dermacentor, Ixodes, Haemaphysalis,Hyalomma, Rhipicentor, Margaropus, Rhipicephalus, Argas, Otobius, andOrnithodorus.

Conveniently, the compounds represented by formula (I) may be preparedby the following reaction sequence: ##STR6## wherein in the abovereaction sequence R₁ and R₂ are as hereinbefore defined and R₃ waschosen to represent CH₃ --.

Thus, ethyl chrysanthemate (II), wherein R₃ is methyl, is oxidized withozone in a methanolic solution at -50° to -70° C. to yield thecorresponding 3-formyl-2,2-dimethylcyclopropanecarboxylic acid ethylester (III). Next, the thus obtained formyl compound is condensed in thepresence of a base, such as sodium ethoxide in a lower alcohol with acompound of formula: R₁ --CH₂ --CN having an active methylene group toyield a cyclopropanecarboxylic acid of formula (IV). This acid isconverted to the corresponding acid chloride (V) with thionyl chloridein an inert aromatic solvent such as benzene, toluene or xylene. Theacid chloride (V) is then reacted with an alcohol of formula R₂ --OH inthe presence of an acid acceptor, such as pyridine, in an inert aromaticsolvent such as benzene, toluene or xylene to afford the desiredcyclopropanecarboxylic esters of formula (I).

Alternatively, formula (I) compounds may be prepared from thecorresponding cyclopropanecarboxylic acids via ester forming reactionspromoted by phase transfer catalysts. The above referred-to reactionsmay be schematically illustrated as follows: ##STR7## wherein in theabove reaction schemes A and B, R₁ is selected from ##STR8## R₃ isselected from hydrogen or methyl; R₄ is ##STR9## M is sodium orpotassium; X and X' are each selected from hydrogen, halogen, C₁ -C₃alkyl, C₁ -C₃ alkoxy and haloalkyl C₁ -C₂ ; Y is selected from hydrogen,halogen, methyl or methoxy; the cis and trans cyclopropane isomers, theE and Z side-chain olefin isomers the optical isomers thereof and theisomeric mixtures thereof.

In the above reactions, the phase transfer catalysts are selected frombenzyltriethylammonium chloride, benzyl-tri-n-propylammonium chloride,α-methylbenzyltriethylammonium iodide, tetrabutylammonium chloride andiodide, methyl tricaprylammonium chloride, hexadecyl trimethylammoniumbromide, benzyl triphenylphosphonium chloride, hexadecyl tributylphosphonium bromide, crown ethers, such as 18-crown-6,dicyclohexyl-18-crown-6 and dibenzo-18-crown-6. These phase transfercatalysts are utilized in amounts of 0.1% to 10% molar quantities andpreferably 5% to 10% molar quantities. Solvents for these reactions areselected from methylene chloride, chloroform, 1,2-dichloroethane,hexane, heptane cyclohexane, benzene, toluene, xylene and ethyl acetate.The above described reactions are further illustrated in the Examplesappended hereto.

Control of Ixodids is achieved by contacting the larvae, nymphs and theadult males and females with the cyclopropanecarboxylic esters offormula (I). Application can be made directly or indirectly. It isgenerally effected by topically applying the active ingredients, namelythe compounds of formula (I) onto the host to be protected or to thehabitat of the Ixodid.

Application is generally facilitated by employing a compositioncontaining an effective amount of a compound of formula (I) incombination with an inert agricultural adjuvant. One or more of theconventional solid or liquid carriers, diluents and formulation aids maybe employed as the adjuvant. Furthermore, in addition to employing asingle compound of formula (I) as the active ingredient, several of theformula (I) compounds, or one or more of the compounds in combinationwith conventional pesticides may be employed.

The compounds of the invention as represented by formula (I) may beconveniently formulated as dusts, dust concentrates, wettable powders,emulsifiable concentrates, and the like. Application thereof is made inconventional manners, such as, by spraying, dusting, dipping in baths,and the like.

Solid formulations such as dusts, dust concentrates, can be prepared bygrinding and blending together an inert solid diluent such asattapulgite, kaolin, walnut shell flour, diatomaceous earth, groundcorncob grits, or ground coconut shell, and the active ingredient wheresuch ingredient is in solid form. Where the active ingredient is aliquid, it may be sprayed on the carrier and thoroughly mixed therewith,or it may be dissolved in a solvent such as acetone, lower alkanol,toluene, xylene and the like, and sprayed as a dilute solution on thesolid carrier. Dusts usually contain from about 1% to 15% by weight ofactive ingredient, whereas concentrates may contain from about 16% toabout 85% by weight of the active material.

Wettable powders are prepared in the same fashion as dust concentratesexcepting that about 5% to 10% by weight of a surfactant is also added.The wettable powder is then generally dispersed in water, or othersuitable diluent for application as a dilute spray onto the Ixodid, hostor locus where control is desired or as a bath for dipping animal hosts.

The formula (I) cyclopropanecarboxylic acid esters may also be preparedas emulsifiable concentrates by dissolving or dispersing about 10% to75% by weight of the active compound in a suitable solvent carrier suchas a petroleum distillate having a minimum aromatic content of 85%, andadmixing therewith about 10% by weight of an emulsifier such aspolyoxyethylene condensates and blends of same with alkyl arylsulfonates. These concentrates are also generally dispersed in water orother suitable solvent for application by spraying or dipping the animalhost.

Application of the formula (I) compounds at rates in the range of fromabout 1 ppm to 250 ppm for the control of ectoparasites, and especiallyIxodidae, is generally preferred.

For the control of insect pests of agriculturally important cropsapplication at rates in the range of from about 10 ppm to 1000 ppm isgenerally preferred.

The following non-limiting Examples further serve to illustrate theinvention.

EXAMPLE 1 Preparation of 3-formyl-2,2-dimethyl-cyclopropanecarboxylicacid, ethyl ester.

A solution of ethyl chrysanthemate (156.0 g) in absolute methanol (1400ml) is stirred, cooled to -65° C., and ozone bubbled in at a rate of 1.7l/min. under 0.56 kg/cm² pressure (the ozone is generated with aWelsbach T-23 ozonator; voltage setting 120 VAC). Durint the reaction,the temperature range of the reaction mixture fluctuates between -65° C.and -50° C.

The reaction is followed with gas chromatography [6'×1/4" glass column,packed with 3% OV-1 on WHP; temperature 130° C.; sample size 0.2λ; flow45 ml/min He; FID detector] to measure the disappearance of ethylchrysanthemate. The ozonolysis is stopped after about 6 to 7 hours whenabout 5% ethyl chrysanthemate is still present. Methyl sulfide (125 ml)is added over 20 minutes, and the reaction mixture allowed to warm up toroom temperature overnight with stirring. Next, the methanol is removedin vacuo at 50°-55° C. The residual oil is diluted with ether, and theether solution washed with water. The ether layer is dried overmagnesium sulfate, filtered, and is then evaporated to yield 131.3 g oftitle product.

An nmr is run on the product to determine if any acetal which may haveformed during the reaction (multiplet at 3.4δ) is present. If acetal isfound in the product, 10% hydrochloric acid (85 ml) is added withstirring followed by the addition of sufficient amount oftetrahydrofuran to obtain a homogeneous solution. The solution is heatedat 40°-50° C. for one hour. Water and ether are added, and the aqueouslayer extracted with ether. The ether layers are combined, dried overmagnesium sulfate and evaporated in vacuo to afford the title product.

EXAMPLE 2 Preparation of (Z)-cis andtrans-3-(β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid.

Phenylacetonitrile is added to a stirred solution of sodium ethoxide inabsolute ethanol (prepared from 1.1 g sodium and 100 ml of ethanol).Next, a solution of 3-formyl-2,2-dimethyl-cyclopropanecarboxylic acidethyl ester (8.5 g) in absolute ethanol (15 ml) is added over 5 minutes.The reaction mixture is stirred for 12 hours at room temperature andthen heated on a steam bath for 0.5 hour. The alcohol is removed invacuo, and the residue washed with water (250 ml) and ether (150 ml).The aqueous layer is acidified with concentrated hydrochloric acid. Theresulting cream colored slurry is filtered and the isolated productdried. The product is dissolved in ether and precipitated with hexane toafford 6.1 g of white crystals, m.p. 186°-188° C.

By the above procedure, a number of cyclopropanecarboxylic acids areprepared. These are listed in Table I below, together with their meltingpoints.

                  TABLE 1                                                         ______________________________________                                        Substituted Cyclopropanecarboxylic Acids                                       ##STR10##                                                                    R.sub.1            m.p. °C.                                            ______________________________________                                         ##STR11##         190-208                                                     ##STR12##         188-198                                                     ##STR13##         120-142                                                     ##STR14##         130-145                                                     ##STR15##         217-218                                                     ##STR16##         140-143                                                     ##STR17##         125-155                                                     ##STR18##         160-180                                                     ##STR19##         179-195                                                     ##STR20##         195-202                                                     ##STR21##         *                                                           ##STR22##         103-112                                                     ##STR23##         150-164                                                     ##STR24##         164-176                                                     ##STR25##         117-123                                                    ______________________________________                                         * = Gum  NMR TMS  CDCL.sub.3 doublet  6.30δ doublet 7.05δ-   

EXAMPLE 3 Preparation of(Z)-trans-3-(β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acidm-phenoxybenzyl ester.

A mixture of (Z)-cis andtrans-3-(β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid (3.5g), benzene, (50 ml), and thionyl chloride (3.4 g) is refluxed for 1hour. The benzene and excess thionyl chloride are then removed in vacuo.The residue is dissolved in benzene and added to a solution ofm-phenoxybenzyl alcohol (2.9 g) in a mixture of benzene (50 ml) andpyridine (1.1 g). The reaction mixture is stirred at room temperaturefor 3 hours, and then filtered. The filtrate is evaporated in vacuo. Theresidue is chromatographed on a silica gel column, and eluted with ethylacetate and hexane to afford the title product.

Analysis calculated for C₂₈ H₂₅ O₃ N: C 79.41; H, 5.95; N 3.31; Found: C78.58; H 6.41; N 2.84.

By the above procedure, a number of cyclopropanecarboxylic acid estersare prepared. These are listed in Table II below, together with thecorresponding analytical data.

                  TABLE II                                                        ______________________________________                                        Cyclopropanecarboxylic acid esters                                             ##STR26##                                                                                           Analysis                                                                            Calcu-                                           R.sub.1   R.sub.2            lated   Found                                    ______________________________________                                         ##STR27##                                                                              CMPB               C 77.66 H  5.39 N  6.24                                                               C 76.65 H  5.71 N  5.88                   ##STR28##                                                                              MPB                C 73.43 H  5.28 N  3.06                                                               C 73.35 H  5.44 N  2.89                   ##STR29##                                                                              CMPB               C 72.12 H  4.80 N  5.80                                                               C 71.44 H  5.25 N  5.03                   ##STR30##                                                                              MPB                C 76.80 H  6.00 N  3.09                                                               C 76.02 H  5.89 N  2.61                   ##STR31##                                                                              CMPB               C 75.29 H  5.48 N  5.86                                                               C 74.93 H  5.35 N  5.68                   ##STR32##                                                                              MPB                C 68.30 H  4.71 N  2.85                                                               C 68.25 H  4.72 N  2.55                   ##STR33##                                                                              CMPB               C 67.32 H  4.29 N  4.90                                                               C 66.64 H  4.46 N  4.90                   ##STR34##                                                                              CMPB               C 79.50 H  5.26 N  5.62                                                               C 79.20 H  5.69 N  5.54                   ##STR35##                                                                              CMPB                --      --                                       ##STR36##                                                                              MPB                C 73.58 H  5.25 N  3.04                                                               C 72.34 H  5.65 N  2.86                   ##STR37##                                                                              CMPB               C 72.12 H  4.80 N  5.80                                                               C 71.47 H  5.10  N  5.42                  ##STR38##                                                                              MPB                C 74.50 H  5.39 N  3.00                                                               C 73.25 H  5.48 N  2.85                   ##STR39##                                                                              CMPB               C 73.16 H  4.91 N  5.69                                                               C 71.59 H  5.22 N  5.33                   ##STR40##                                                                              MPB                C 66.93 H  4.81 N  2.79                                                               C 66.33 H  4.97 N  2.64                   ##STR41##                                                                              CMPB               C 66.04 N  4.40 N  5.31                                                               C 65.58 H  4.74 N  4.95                   ##STR42##                                                                              MPB                C 68.30 H  4.71 N  2.85                                                               C 68.60 H  4.84 N  2.58                   ##STR43##                                                                              CMPB               C 67.32 H  4.29 N  5.42                                                               C 66.55 H  4.64 N  5.13                   ##STR44##                                                                              MPB                C 73.44 H  5.28 N  3.06                                                               C 73.12 H  5.25 N  2.71                   ##STR45##                                                                              CMPB               C 72.12 H  4.80 N  5.80                                                               C 70.85 H  5.03 N  5.22                   ##STR46##                                                                              MPB                C 68.30 H  4.71 N  2.85                                                               C 67.83 H  4.98 N  2.59                   ##STR47##                                                                              CMPB               C 67.32 H  4.29 N  5.41                                                               C 65.13 H  4.11 N  5.14                   ##STR48##                                                                              MPB                C 76.17 H  5.48 N  2.86                                                               C 75.29 H  5.63 N  2.80                   ##STR49##                                                                              MPB                C 76.17 H  5.48 N  2.86                                                               C 76.52 H  5.61 N  2.69                   ##STR50##                                                                              CMPB               C 74.67 H  4.97 N  6.00                                                               C 74.64 H  5.15 N  5.90                   ##STR51##                                                                              MPB                C 79.61 H  6.22 N  3.20                                                               C 79.39 H  6.44 N  3.01                   ##STR52##                                                                              MPB                C 79.61 H  6.22 N  3.20                                                               C 79.33 H  6.22 N  2.85                   ##STR53##                                                                              CMPB               C 77.90 H  5.67 N  6.06                                                               C 74.54 H  5.36 N  5.63                   ##STR54##                                                                               ##STR55##         C 74.67 H  4.97  N  6.00                                                              C 74.32 H  5.11 N  5.55                   ##STR56##                                                                               ##STR57##         C 75.30 H  5.48 N  5.85                                                               C 74.02 H  5.49 N  5.84                   ##STR58##                                                                               ##STR59##         C 72.11 H  4.80 N  5.80                                                               C 72.43 H  4.97 N  5.52                  ______________________________________                                         ##STR60##                                                                     ##STR61##                                                                

EXAMPLE 4 Preparation of 2-Formyl-3-methylcyclopropanecarboxylic acidethyl ester.

Crotonaldehyde (14.0 g; 0.2 mole) is added dropwise to a gentlyrefluxing solution of tetrahydrothiophene ylid (34.0 g; 0.2 mole) in dryacetone (200 ml). Heating at reflux is continued for about 15 minutesafter the addition is completed, then the reaction mixture isconcentrated on a rotary evaporator at 50° C. Distillation of thisconcentrate at reduced pressure affords 15.32 g (49.1%) of titleproduct, a pale yellow oil, b.p. 0.1 mm, 44°-45° C. The structure isconfirmed by IR and NMR.

EXAMPLE 5 Preparation of (Z)-cis andtrans-2-(β-cyanostyryl)-3-methylcyclopropanecarboxylic acid.

A solution of sodium ethoxide is prepared by adding sodium spheres (1.15g, 0.05 mole) to absolute ethanol (100 ml) with stirring until asolution is obtained. Phenylacetonitrile (5.86 g, 0.05 mole) and2-formyl-3-methylcyclopropanecarboxylic acid methyl ester (7.81 g, 0.05mole) are added to the above solution at room temperature. The resultantclear solution is stirred for 18 hours at room temperature, then heatedat reflux for about 0.5 hours. The reaction mixture is then cooled,evaporated in vacuo, and the residue dissolved in water. The aqueoussolution is extracted (3X) with ether and is then acidified withconcentrated hydrochloric acid. A brown solid precipitates and isisolated by filtration and dried to afford 8.78 g (77.3%) of a tackybrown solid. NMR data supports the presence of both isomers (the olefinproton of the two isomers appearing as doublets at 6.17 ppm and 6.96ppm).

EXAMPLE 6 Preparation of (Z)-cis andtrans-2-(β-cyanostyryl)-3-methylcyclopropanecarboxylic acid,α-cyano-m-phenoxybenzyl ester.

By the procedure of Example 3, (Z)-cis andtrans-2-(β-cyanostyryl)-3-methylcyclopropanecarboxylic acid (5.0 g,0.022 mole) is reacted with thionyl chloride (d=1.63; 1.75 ml), 0.24mole), and when formation of the acid chloride is complete, it (the acidchloride) is further reacted with a mixture of α-cyano-m-phenoxybenzylalcohol (4.5 g, 0.02 mole) and pyridine (1.74 g, 0.022 mole) to yield acrude, gummy product. The crude is purified by dry column chromatographytography silica gel; 1:1 methylene chloride (hexane) to give 4.8 g(57.1%) of a yellow gum.

Analysis calculated for C₂₈ H₂₂ N₂ O₃ : C 77.40; H 5.10; N 6.45; Found:C 76.30; H 5.23; N 6.24.

EXAMPLE 7 Preparation of (Z)-cis andtrans-3-(β-cyano-p-methylstyryl)-2,2-dimethyl-cyclopropanecarboxylicacid, m-phenoxybenzyl ester.

m-Phenoxybenzylbromide (3.68 g; 0.014 mole) is added to a solution of3-(β-cyano-p-methylstyryl)-2,2-dimethylcyclopropanecarboxylic acid (3.19g; 0.0125 mole) and triethylamine (1.27 g; 0.0125 mole) in drydimethylformamide and the reaction mixture stirred for 18 hours at roomtemperature. The reaction mixture, containing some precipitated salts,is poured into water and extracted with ether (2×75 ml). The combinedether extracts are washed several times with water, then with sodiumbicarbonate solution and saturated sodium chloride solution. Evaporationof the ether solution yields 3.42 g (62.5%) of a yellow oil.Purification of this yellow oil by dry column chromatography (silicagel; eluent: 1:1 methylene chloride:hexane) affords 0.96 g of the transisomer and 0.6 g of the cis isomer.

Analysis calculated for C₂₉ H₂₇ NO₃ : C 79.61; H 6.22; N 3.20; (trans)Found: C 79.39; H 6.44; N 3.01; (cis) Found: C 79.33; H 6.53; N 2.85.

EXAMPLE 8 Preparation of (Z)-cis andtrans-3-(β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid,α-cyano-m-(p-chlorophenoxy)benzyl ester by a phase transfer catalystesterification process.

Thionyl chloride (1.61 ml, 2.6 g; 0.022 mole),3-(β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid (4.82 g; 0.02mole) and toluene are mixed and heated at 100° C. for 1 hour. Thereaction mixture is cooled to 25° C. and a solution ofm-(p-chlorophenoxy)benzaldehyde (4.65 g; 0.02 mole) and 18-crown-6 (0.49g; 0.002 mole) in toluene (10 ml) is added. To this reaction mixture asolution of potassium cyanide (2.6 g; 0.04 mole) in water (6 ml) isadded slowly while maintaining the temperature between 20°-25° C. Thereaction mixture is then stirred for 18 hours at room temperature. Theresultant black reaction mixture is poured in water and extracted withether (3×). The combined ether extracts are washed with water, 10%hydrochloric acid, 10% sodium bicarbonate, water and saturated sodiumchloride solution. The ether layer is dried over sodium sulfate andevaporated in vacuo to leave a brown gum. This gum is purified by drycolumn chromatography (silica gel; eluent: 1:1 methylenechloride:hexane) to afford the title product, a yellow glass (1.0 g,8.6%).

Analysis calculated for C₂₉ H₂₃ ClN₂ O₃ : C 72.12; H 4.80; N 5.80;Found: C 72.43; H 4.97; N 5.53.

EXAMPLE 9 Preparation of 20% w/w emulsifiable concentrates containingcyanovinyl pyrethroids of the invention. Toxicants

(1).(Z)-trans-3-(p-chloro-β-cyanostyryl)-2,2-dimethylcyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester.

(2). (Z)-trans-3-(β-cyanostyryl)-2,2-dimethylcyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester.

(3).(Z)-trans-3-(2,4-dichloro-β-cyanostyryl)-2,2-dimethylcyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester.

Concentrates

    ______________________________________                                        Component               wt. in g.                                             ______________________________________                                        Toxicant                15.0                                                  Atlox®   3403F/3404F; 50:50 mixture.sup.(a)                                                       10.125                                                xylene                  6.75                                                  "HAN".sup.(b)           35.625                                                Total:                  67.500                                                ______________________________________                                         .sup.(a) Atlox® 3403F, a polyoxyethylene alkyl aryl ether  alkyl aryl     sulfonate blend; nonionic surfactant; specific gravity: 1.02 at 20.degree     C.; wt in kg/l = 1.018 (8.5 lb/gal); approximate viscosity at 25°      C. = 130 cps; flash point (C.O.C.; °F.) = 100; Atlox® 3403F, a     polyoxyethylene ether polyoxyethylene glyceride  alkyl aryl sulfonate         blend; anionic surfactant; specific gravity 1.05 at 25° C.; wt in      kg/l = 1.052 (8.7 lb/gal); approximate viscosity at 25° C. = 3700      cps; flash point (C.O.C.; °F.) = 160. Both are proprietary product     of ICI United States Inc. Atlas Chemicals Division, Wilmington, Delaware.     .sup.(b) "HAN" = Heavy Aromatic Naphtha, boiling range 165° C. to      282° C.; Mixed aniline point °C. = 28.0; freeze point           °C. = 36; aromatic content: 80%.                                  

Method of preparation.

The toxicant is preheated to about >85° C. to obtain a flowable melt,and then mixed with the surfactants, xylene and "HAN". The resultantmixture is heated and stirred to obtain a clear solution.

Standard emulsification test (50 λ/33 ml medium hard water) indicates,that although on addition the emulsifiable concentrate tends to float ontop of the water layer, with agitation (or shaking) good emulsions areobtained, which remain quite stable with very little creaming on top.

The average micelle sizes of the aqueous emulsions prepared from theabove concentrates are determined using a Coulter Counter with thefollowing results:

    ______________________________________                                        Emulsion containing toxicant No.                                                                 Micelle size in microns                                    ______________________________________                                        1                  4.5                                                        2                  2.2                                                        3                  2.4                                                        ______________________________________                                    

EXAMPLE 10 Evaluation of the efficacy of the compounds of the inventionfor the control of Boophilus microplus larvae.

Effective control of acarina larvae is demonstrated in the followingtests with larvae of Boophilus microplus, a one-host tick which canremain on a single host through its three life stages, i.e. larva, nymphand adult. In these tests a 10% acetone/90% water mixture contains thetest compound at the concentrations indicated in Table III below. Twentylarvae are enclosed in a pipet sealed at one end with a gauze material,and a solution, containing the test compound at the concentrationsgiven, is then drawn through the pipet with a vacuum hose simulating aspray system. The ticks are then held for 48 hours at room temperature,and percent mortality rates are then determined. The results obtainedwith the various compounds are tabulated in Table III below.

                                      TABLE III                                   __________________________________________________________________________    Efficacy of cyanovinyl pyrethroids for the control of                         Boophilus microplus larvae.                                                    ##STR62##                                                                                                  Concentration of                                                                       Percent Mortality                                                    Toxicant in spray                                                                      of Boophilus                           R.sub.1                   R.sub.2                                                                           solution (ppm)                                                                         microplus larvae.                      __________________________________________________________________________     ##STR63##                CMPB                                                                              0.001    100                                     ##STR64##                MPB 0.001    100                                     ##STR65##                CMPB                                                                              0.001    100                                     ##STR66##                MPB 1.0      100                                     ##STR67##                CMPB                                                                              1.0      100                                     ##STR68##                MPB 0.001    100                                     ##STR69##                CMPB                                                                              0.001    100                                     ##STR70##                CMPB                                                                              100.0    100                                     ##STR71##                MPB 100      100                                     ##STR72##                MPB 100      100                                     ##STR73##                MPB 10       100                                     ##STR74##                MPB 100      30                                      ##STR75##                MPB 100      100                                     ##STR76##                MPB 100      0                                       ##STR77##                    1.0 0.1  100  50                                __________________________________________________________________________     ##STR78##                                                                     ##STR79##                                                                

EXAMPLE 11 Suppression of fecundity and chemosterilant effect inIxodidae.

The efficacy of the compounds of the invention for suppression offecundity and chemosterilant effect in ticks is demonstrated in thefollowing tests wherein engorged adult female Boophilus microplus,multiple resistant strain, ticks which have dropped from cattle arecollected and used for testing.

The compound to be tested is dissolved in a 35% acetone/65% watermixture in amounts sufficient to provide the concentrations indicated inTable IV below. Ten ticks per treatment are used and they are immersedin the test solution for three to 5 minutes, then removed and held inincubators for two to three weeks at 28° C. Counts of ticks laying eggsare then made and recorded. Eggs which were laid are placed incontainers and kept for one month to observe hatching and to determinechemosterilant effect. Results of these tests are given in Table IVbelow.

                  TABLE IV                                                        ______________________________________                                        Efficacy of cyanovinyl pyrethroids expressed as % reduction                   of viable egg masses.                                                          ##STR80##                                                                                                    Percent reduction                                                Concentration in                                                                           of viable egg                                 R.sub.1    R.sub.2 solution (ppm)                                                                             masses                                        ______________________________________                                         ##STR81## CMPB    31.2 16.0 8.0 8.0 4.0                                                                      95.9-99 85 65 84-94 62-70                      ##STR82## MPB     15 8 4       99.4 72.9-78 24.5-32                           ##STR83## CMPB    4 2          99.4 97                                        ##STR84## MPB     250 125 62 31                                                                              85.5-87.8 79.1-91.2 90.9-96.6 63.6             ##STR85## CMPB    31  15       91.8 73.5                                      ##STR86## MPB     32 16 8      85.6-91 87.5-95 40-64                          ##STR87## CMPB    4 2          97 55                                          ##STR88## CMPB    31           98.8                                           ##STR89## CMPB    15           92                                             ##STR90## CMPB    100          100                                           ______________________________________                                         ##STR91##                                                                     ##STR92##                                                                

EXAMPLE 12 Evaluation of the efficacy of cyanovinyl pyrethroids for thecontrol of Boophilus microplus on cattle. Test Compounds

The 20% w/w emulsifiable concentrates of Example 6 are used in thisexperiment. Spray emulsions are prepared just prior to use from theabove concentrates by diluting 11.25 ml and 22.5 ml of each with 75liter of water to yield spray emulsions containing 30 and 60 ppm ofactive ingredient, respectively.

Test Animals

Holstein calves, 6 to 12 months old are experimentally infested withabout 5000 larval ticks of a multiple resistant (resistant toorganophosphate acaricides as well as to toxaphene and lindane) strainplaced on each animal three times a week, starting 35 dayspre-treatment. Three pre-treatment tick counts are made in days -6, -5and -4. Calves are allocated to groups of five on the basis of thesecounts. One group serves as infected nontreated controls and one groupeach is used to evaluate the test compounds at 30 and 60 ppm level oftoxicant, respectively. On treatment day, each animal is sprayed with atotal of 15 liters of emulsion delivered at 21.09 kg/cm² pressure with a"Teejet 8002 Excelsior" nozzle providing a fan-shaped spray. Mortalitycounts (female ticks 4.5-8.0 mm) are taken over days 2 to 21posttreatment for a total of 9 times. Residual effect is measured by sixmortality counts taken over days 23 to 35 posttreatment. The resultsobtained, are summarized and tabulated in Table V below.

                  TABLE V                                                         ______________________________________                                        Evaluation of the efficacy of the compounds of the present                    invention for the control of multiple resistant ticks on                      cattle.                                                                        ##STR93##                                                                            Toxiant   Percent Mortality                                                   Concentration                                                                           (post-treatment)                                            R.sub.1    (ppm)      Days 2 to 21                                                                              Days 23 to 35                               ______________________________________                                         ##STR94##                                                                                30 60       95.8 99.2   97.8 99.4                                  ##STR95##                                                                                30 60       92.9 96.8   99.2 99.2                                  ##STR96##                                                                                30 60       65 85.9     89.2 95.5                                 ______________________________________                                    

EXAMPLE 13 Evaluation of the Ixodicidal activity of cyanovinylPyrethroids against Amblyomma hebreum.

The ixodicidal activity of the compounds of the invention isdemonstrated in the following tests wherein juvenile adult Amblyommahebreum ticks are collected and used for testing.

The compound to be tested is dissolved in a 35% acetone/65% watermixture in amounts sufficient to provide the concentrations indicated inTable VI below. Ten ticks per treatment (ten males or ten females) areused and they are immersed in the test solution for three to 5 minutes,then removed and held in incubators at 28° C. Percent mortality isdetermined at 24 and 96 hours post-immersion. The data obtained istabulated in Table VI below.

                  TABLE VI                                                        ______________________________________                                        Percent Mortality of Amblyomma hebreum at 24 hours post-                      immersion.                                                                     ##STR97##                                                                             Concentration                                                                 of Toxicant % Mortality                                              R.sub.1   (ppm)      at 24 hours                                                                              Remarks                                       ______________________________________                                         ##STR98##                                                                               240 120  60 30 15  7.5  3.25                                                              100 100  90 45  6 15  0                                                                100% at 96 hours  75% at 96 hours              ##STR99##                                                                               240 120  60 30 15  7.5  3.25                                                               95 70 45 75 15  0  0                                   ##STR100##                                                                              240 120  60 30 15  7.5 3.25                                                               100 100  65 60 50  0  0                                ______________________________________                                    

EXAMPLE 14 Evaluation of the efficacy of the compounds of the inventionfor the control of face flies (Musca autumnalis).

The cyanovinyl pyrethroids in these tests are dissolved in acetone toafford stock solutions at a concentration of 1000 ppm each.

One kg of fresh, untreated cow manure and the appropriate volume of thestock solution of the pyrethroid used in the test are mixed for twominutes with a Hobart heavy duty mixer to yield a blend containing thetoxicant at the ppm concentration indicated in Table VII below. Controlsamples are prepared similarly using the corresponding volumes ofacetone (no toxicant). Two 148 cm³ (5-oz) plastic dixie cups are thenmounded full of treated or untreated manure. A small reservoir is madein the top of the manure, and into this reservoir are placed twentytwo-day old Musca autumnalis larvae. The larvae are then covered withthe same manure. Each cup is placed in an individual sand tray forpupation, and maintained for 5 days. At the end of the period mortalitycounts are made. The results are given in Table VII below.

                  TABLE VII                                                       ______________________________________                                        Activity of Cyanovinyl pyrethroids for the control of                         Musca autumnalis                                                               ##STR101##                                                                                      Concentration                                                                             Percent Mortality of                           R.sub.1    R.sub.2  (ppm)      Musca autumnalis                               ______________________________________                                         ##STR102##                                                                              CMPB      1 0.1        100  88                                      ##STR103##                                                                              MPB       10           100                                          ##STR104##                                                                              MPB       10           100                                          ##STR105##                                                                              CMPB      1 0.1         83 100                                      ##STR106##                                                                              MPB       10            70.8                                        ##STR107##                                                                              CMPB      10           100                                          ##STR108##                                                                              MPB       10           100                                          ##STR109##                                                                              CMPB      10            94.7                                       ______________________________________                                         ##STR110##                                                                    ##STR111##                                                               

EXAMPLE 15 Evaluation of cyanovinyl pyrethroids for the control ofScrewworm fly (Cochliomyia hominivorax) larvae. Screwworm Larvae

Newly hatched larvae are obtained after incubation of 100-120 mg eggmasses placed on filterpaper, wetted with isotonic saline solutions inpetri dishes, and kept at 27° C. and 80%-90% RH for 12-15 hours. Thehatched larvae are reared on the following medium and maintained at 37°C.:

    ______________________________________                                        Lean ground beef      57.0 g                                                  Bovine plasma         21.4 ml                                                 Water                 21.3 ml                                                 Formalin              0.3 ml                                                  Total:                100.0                                                   ______________________________________                                    

After 48 hours, larvae are transferred to trays containing a slightlydifferent medium and maintained in a water bath at 39°-40° C.:

    ______________________________________                                        Lean ground beef       40.0 g                                                 Citrated bovine blood  20.0 ml                                                Water                  39.7 ml                                                Formalin               0.3 ml                                                 Total:                 100.0                                                  ______________________________________                                    

Two ml of an acetone-water solution, containing 10 times the finaldesired concentration of toxicant, is mixed with 18 g of nutritionalmedium in a 60-ml jar. The mixture is kept in a water bath at 39°-40° C.for about 30 minutes, i.e., until the medium reaches the sametemperature. Then masses of 200-300 newly hatched screwworm larvae addedto each jar containing the toxicant mixed with the nutritional medium.Larvae are picked up with a cardboard spatula from the petri dish wherethey had been incubated. Special care is taken to place larval massesover an "island" in the plasma medium. A new spatula is used for eachconcentration of toxicant. The jars are covered with a piece of muslinand kept in a water bath at 40° C. to the end of the experiment. Tworeplicates are used per concentration. Controls containing no toxicantbut the highest concentration of acetone in the nutrient medium are keptfor each experiment.

Final check, by visual inspection is made on the surface of the mediaafter 48 hours, and the approximate percent mortality determined.

The results obtained are averaged and tabulated in Table VIII below.

                  TABLE VIII                                                      ______________________________________                                        Efficacy of cyanovinyl pyrethroids expressed as percent                       mortality of Screwworm Fly larvae.                                             ##STR112##                                                                                     Concentration                                                                             Percent Mortality                                                 of toxicant of Screwworm Fly                                R.sub.1  R.sub.2  (ppm)       larvae (approximate)                            ______________________________________                                         ##STR113##                                                                            CMPB     25  5       100  21.1                                        ##STR114##                                                                            MPB      25           34.1                                            ##STR115##                                                                            CMPB     25  5        90  7                                           ##STR116##                                                                            CMPB     25           7.3                                            ______________________________________                                         ##STR117##                                                                    ##STR118##                                                               

EXAMPLE 16 Evaluation of the siphonaptericidal activity of cyanovinylpyrethroids.

The siphonaptericidal activity of the compounds of this invention isdemonstrated by the following tests wherein the cyanovinyl pyrethroidslisted in Table IX below are utilized as the active ingredients. Inthese tests, ten adult fleas of the species Ctenocephalides felis aresprayed for 30 seconds with an acetone/water solution containing 50 and10 ppm of the test compound, respectively. After this treatment, thefleas are maintained for 48 hours at room temperature and 80+% relativehumidity. At the end of this period the fleas are examined and mortalitycounts made. The results are tabulated in Table IX below.

                  TABLE IX                                                        ______________________________________                                        Activity of cyanovinyl pyrethroids against Ctenocephalides                    felis.                                                                         ##STR119##                                                                               Concentration                                                                 of toxicant  Percent Mortality of                                 R.sub.1     (ppm)        Ctenocephalides felis                                ______________________________________                                         ##STR120##    50 10          100 45                                           ##STR121##    50 10          100 100                                          ##STR122##    50 10           90 100                                         ______________________________________                                    

EXAMPLE 17 Insecticide testing procedures Malaria Mosquito (Anophelesquadrimaculatus say) egg and larvae test

One ml of a 300 ppm solution is pipetted into a 400 ml beaker containing250 ml of deionized water and stirred with the pipette, giving aconcentration of 1.2 ppm. A wax paper ring 0.6 cm wide to fit inside thebeaker is floated on the surface of the test solution to keep the eggsfrom floating up the meniscus curve and drying out on the side of theglass. A spoon made of screen is used to scoop up and transfer about 100eggs (0-24 hours old) into the test beaker. After two days at 26.7° C.observations of hatching are made. This includes kill of eggs orinhibition of hatch, kill of newly hatched larvae, or delayed hatch.Additional observations are made after another day for the same effects.

Tobacco Budworm [Heliothis virescens (Fabricius)]

A cotton plant with 2 true leaves expanded is dipped for 3 seconds withagitation in a 300 ppm solution. A 1.25 to 2 cm square of cheeseclothwith about 50 to 100 budworm eggs 0-24 hours old is also dipped in thetest solution and placed on one leaf to dry. The leaf with the treatedbudworm eggs is removed from the plant and placed in a 236.6 ml (8-oz)Dixie cup with a wet 5 cm piece of dental wick and covered with a lid.The other leaf is placed in a similar cup with a wick and a piece ofcheesecloth infested with 50-100 newly hatched larvae is added beforecovering the cup with a lid. After 3 days at 26.7° C., observations ofegg hatch are made as well as kill of newly hatched larvae, anyinhibition of feeding, or interference of any sort with normaldevelopment.

Phosphate-Resistant Strain of Two-Spotted Spider Mite [Tetranychusurticae (Koch)]

Sieva lima bean plants, with primary leaves 7.6 to 10 cm long, areinfested with about 100 adult mites per leaf 4 hours before use in thistest, in order to allow egg-laying before treatment. The infested plantsare dipped for 3 seconds with agitation into a 300 ppm solution, and theplants set in the hood to dry. After 2 days at 26.7° C., the adult mitemortality is estimated on one leaf under a 10X stereoscopic microscope.The other left is leaf on the plant an additional 5 days and thenexamined at 10X power to estimate the kill of eggs and of newly-hatchednymphs, giving a measure of ovicidal and residual action, respectively.

Southern Armyworm [Spodoptera eridania (Cramer)]

A Sieva lima bean plant with just the primary leaves expanded to 7.6 to10 cm is dipped for 3 seconds with agitation in a 1000 ppm solution andset in a hood to dry. Following this, one leaf is placed in a 10 cmpetri dish which has a moist filter paper in the bottom and 10third-instar armyworm larvae about 1 cm long. The dish is covered andheld at 26.7° C. After 2 days mortality counts and estimates of theamount of feeding are made. Compounds showing partial kill and/orinhibition of feeding are held for an extra day for furtherobservations.

All compounds showing activity as defined above are retested, using thesecond leaf on the bean plant, after an interval of 7 days from originaltreatment, as an assay of residual activity.

Mexican Bean Beetle (Epilachna varivestis Mulsant)

Sieva lima bean plants (2 per pot) with primary leaves 7.6 to 10 cmlong, are dipped in a 300 ppm solution and set in a hood to dry. Oneleaf is removed from the plant and placed in a 10 cm petri dishcontaining a moist filter paper on the bottom and 10 last-instar larvae(13 days from hatching).

The day after treatment, another leaf is removed from the plant and fedto the larvae after removing the remains of the original leaf. Two daysafter treatment, the third leaf is fed to the larvae, this usually beingthe last needed. The fourth leaf is used on the third day aftertreatment if the larvae have not finished feeding. The test is now setaside and held until adults have emerged, usually about 9 days aftertreatment began. After emergence is complete, each dish is examined fordead larvae, pupae or adults; deformed pupae or adults; larval-pupalintermediates or pupal-adult intermediates; or any other interferencewith normal molting, transformation and emergence of pupae or adults.

Western Potato Leaf Hopper (Empoasca abrupta DeLong)

A lima bean plant with the primary leaf expanded to 7.6 to 10 cm isdipped into a 100 ppm solution and set in a hood to dry. A 2.5 cm pieceof the tip of 1 leaf is cut off and placed in a 10 cm petri dish with amoist filter paper in the bottom. (In practice, this is usually cut offthe tip of a plant from the Mexican bean beetle tests using a bean leafdipped in the needed solution). From 3 to 10 second-instar nymphs aretapped from the culture plants into the test dish and rapidly covered.Mortality counts are made after two days at 26.7° C.

Malaria Mosquito (Anopheles quadrimaculatus Say) Adult Test

Ten ppm solutions are poured into wide-mouth 46.2 ml jars eachcontaining a microscope slide. The slides are removed from the testsolution with forceps and laid horizontally to dry on a wide-mouth 118.4ml bottle. When dry, they are placed in the same 118.4 ml bottle and ten4 to 5-day old mosquitoes of mixed sexes are added to each bottle. Apiece of cotton gauze held on by an elastic band serves as a lid and awad of cotton soaked in 10% honey solution serves as food. Mortalitycounts are made after 1 day at 26.7° C.

Bean Aphid (Aphid fabae Scopoli)

Five cm fiber pots, each containing a nasturtium plant 5 cm high andinfested with 100 to 500 aphids 2 days earlier are placed on a 4 rpmturntable and sprayed with a 100 ppm solution for 2 revolutions with aNo. 154 DeVilbiss Atomizer at 1.4 kg/cm² air pressure. The spray tip isheld about 15 cm from the plants and the spray directed so as to givecomplete coverage of the aphids and the plants. The sprayed plants arelaid on their sides on white enamel trays. Mortality estimates are madeafter 1 day at 26.7° C.

Tobacco Budworm [Heliothis virescens (Fabricius)]. Third instar.

Three cotton plants with just expanded cotyledons are dipped in a 1000ppm solution, and placed in a hood to dry. When dry, each cotyledon iscut in half and 10 are each placed in a 29.6 ml plastic medicine cupcontaining a 1.25 cm dental wick saturated with water, and onethird-instar budworm larva is added. The cup is capped and held for 3days at 26.7° C., after which mortality counts are made.

Cabbage Looper. [Trichoplusia ni (Hubner)]

A primary leaf of a cotton plant is dipped in the test solution andagitated for 3 seconds. It is then set in a hood to dry. Following this,the leaf is placed in a 10 cm petri dish containing a moist filter paperat the bottom and 10 third-instar loopers. The dish is covered and heldat 26.7° C. After 2 days, mortality counts and estimates of feedingdamage are recorded. Those materials showing partial kill and/orinhibition of feeding are held for another day for further observations.

The rating system employed in these tests is as follows:

Rating System

0=0-40% killed or affected

1=reduced feeding (trace to light damage)

2=some deformed insects (40-80%)

3=mostly deformed insects (85-100%)

4=not an index number at present

5=41-60% mortality

6=61-70% mortality

7=71-85% mortality

8=86-95% mortality

9=100% mortality

The absence of a number indicates that no test has been run at thatparticular dosage.

Compounds rated active (8 or 9) are further tested at reducedconcentrations in 50% acetone:50% water.

Data obtained are reported in Table X below.

                  TABLE Xa                                                        ______________________________________                                        Insecticide evaluation                                                         ##STR123##                                                                              Mosquito Tobacco Budworm                                                      Larvae ppm                                                                             Eggs (ppm)                                                                              Larvae (ppm)                                    R.sub.1  R.sub.2 1.2   0.4 0.04 300 100 10                                                                            300 100 10                            ______________________________________                                         ##STR124##                                                                            CMPB    9     9   9     8  0    9  9 0                                ##STR125##                                                                            MPB     9     9   0     8  0    9  8 0                                ##STR126##                                                                            MPB     8     6   0     0       9  9 0                                ##STR127##                                                                            CMPB    9     9   0     0       9  9 5                                ##STR128##                                                                            CMPB    9     9   9     8   0   7  0                                 ______________________________________                                         ##STR129##                                                                    ##STR130##                                                               

                                      TABLE Xb                                    __________________________________________________________________________     ##STR131##                                                                                   2-Spotted                                                                             Southern                                                                              Mexican Bean                                                  Spider Mites                                                                          Armyworms                                                                             Beetle                                                        ppm     ppm     ppm                                           R.sub.1     R.sub.2                                                                           300 100 1000                                                                             100                                                                              10                                                                              300                                                                              100                                                                              10                                      __________________________________________________________________________     ##STR132## CMPB                                                                              9   0   9  9  0                                                ##STR133## MPB 9   0   9  0                                                   ##STR134## CMPB                                                                              9   0   1  0    9  8  0                                        ##STR135## CMPB                                                                              0       0       9                                              ##STR136## CMPB                                                                              0       9  5  0 9  9  0                                       __________________________________________________________________________     ##STR137##                                                                    ##STR138##                                                               

                                      TABLE Xc                                    __________________________________________________________________________     ##STR139##                                                                                  Leaf hopper                                                                          Mosquito                                                                             Bean Aphids                                                                          Tobacco Budworm                                                                         Cabbage Looper                                 (ppm)  Adult (ppm)                                                                          (ppm)  3rd Instar (ppm)                                                                        (ppm)                           R.sub.1   R.sub.2                                                                            100 10     1  100                                                                              10                                                                              1 1000 100  1000 100                        __________________________________________________________________________     ##STR140##                                                                             CMPB 9   7  7   0  9  6 0 6    7    9    5                           ##STR141##                                                                             MPB  9   7  7   0  9  7 0 8    0    0    0                           ##STR142##                                                                             MPB  9   0  5   0  9  8 0 5    0    9    1                           ##STR143##                                                                             CMPB 9   5  5   0  9  9 9 8    1    9    9                           ##STR144##                                                                             MPB  5   0  0      9  5   5    0    5    0                           ##STR145##                                                                             CMPB 7   0  0      9  6   0              0                           ##STR146##                                                                             CMPB 9   7  0      9  8 0      0    --                               ##STR147##                                                                             CMPB 7      0      8  0   1         0                                ##STR148##                                                                             CMPB 7      0      7      0         9    9                          __________________________________________________________________________     ##STR149##                                                                    ##STR150##                                                               

I claim:
 1. A compound of the formula: ##STR151## wherein R₁ is##STR152## R₃ is hydrogen or methyl; and X and X' are each hydrogen,halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or haloalkyl C₁ -C₃.
 2. A compoundaccording to claim 1, wherein R₁ is ##STR153## and R₃ is methyl.
 3. Thecompound according to claim 1,(Z)-trans-3-(β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid,α-cyano-m-phenoxybenzyl ester.
 4. The compound according to claim 1,(Z)-trans-3-(β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylic acid,m-phenoxybenzyl ester.
 5. The compound according to claim 1,(Z)-trans-3-(p-chloro-β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylicacid, m-phenoxybenzyl ester.
 6. The compound according to claim 1,(Z)-trans-3-(p-chloro-β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester.
 7. The compound according to claim1,(Z)-trans-3-(β-cyano-p-methoxystyryl)-2,2-dimethyl-cyclopropanecarboxylicacid, m-phenoxybenzyl ester.
 8. The compound according to claim 1,(Z)-trans-3-(β-cyano-p-methoxystyryl)-2,2-dimethyl-cyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester.
 9. The compound according to claim1,(Z)-trans-3-(2,4-dichloro-β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylicacid, m-phenoxybenzyl ester.
 10. The compound according to claim 1,(Z)-trans-3-(2,4-dichloro-β-cyanostyryl)-2,2-dimethyl-cyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester.
 11. The compound according to claim1,(Z)-trans-3-[2-cyano-2(2-naphthyl)vinyl]-2,2-dimethyl-cyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester.
 12. A method for the control ofinsect pests of agriculturally important crops or ectoparasites ofdomesticated warm-blooded animals comprising contacting the insects,ectoparasites or applying to their hosts and to their habitat aninsecticidally or ectoparasiticidally effective amount of a compound ofthe formula: ##STR154## wherein R₁ is ##STR155## R₂ is a moiety##STR156## R₃ is hydrogen or methyl; and X and X' are each hydrogen,halogen, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or haloalkyl C_(1-C) ₂.
 13. Amethod according to claim 12, wherein R₁ is ##STR157## R₂ is ##STR158##R₃ is methyl.
 14. A method according to claim 12 wherein the compoundsare applied to insect pests of agricultural crops, to the foliage andstems of the crops or to the soil in which the crops propagate and growin amounts of from 10 ppm to 1000 ppm.
 15. A method according to claim12, wherein the compounds are applied at the rate of from 1 ppm to 250ppm to the ectoparasites, to their host or to their habitat.
 16. Amethod according to claim 12, wherein the ectoparasites are Ixodidticks.
 17. A method according to claim 16, wherein the compound is(Z)-trans-3-(β-cyanostyryl)-2,2-dimethylcyclopropanecarboxylic acid,α-cyano-m-phenoxybenzyl ester, and the compound is applied in amounts offrom 0.001 ppm to 100 ppm.
 18. A method according to claim 16, whereinthe compound is(Z)-trans-3-(p-chloro-β-cyanostyryl)-2,2-dimethylcyclopropanecarboxylicacid, m-phenoxybenzyl ester, and the compound is applied at a rate of0.001 ppm to 100 ppm.
 19. A method according to claim 16, wherein thecompound is(Z)-trans-3-(p-chloro-β-cyanostyryl)-2,2-dimethylcyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester, and the compound is applied at arate of 0.001 ppm to 100 ppm.
 20. A method according to claim 16,wherein the compound is(Z)-trans-3-(β-cyano-p-methoxystyryl)-2,2-dimethylcyclopropanecarboxylicacid, m-phenoxybenzyl ester, and the compound is applied at a rate of0.001 ppm to 100 ppm.
 21. A method according to claim 16, wherein thecompound is(Z)-trans-3-(β-cyano-p-methoxystyryl)-2,2-dimethylcyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester, and the compound is applied at arate of 0.001 to 100 ppm.
 22. A method according to claim 16, whereinthe compound is(Z)-trans-3-(2,4-dichloro-β-cyanostyryl)-2,2-dimethylcyclopropanecarboxylicacid, m-phenoxybenzyl ester.
 23. A method according to claim 16, whereinthe compound is(Z)-trans-3-(2,4-dichloro-β-cyanostyryl)-2,2-dimethylcyclopropanecarboxylicacid, α-cyano-m-phenoxybenzyl ester.